CN105149611A - Hollow precious metal nanowire as well as preparation method and application thereof - Google Patents
Hollow precious metal nanowire as well as preparation method and application thereof Download PDFInfo
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- CN105149611A CN105149611A CN201510599913.4A CN201510599913A CN105149611A CN 105149611 A CN105149611 A CN 105149611A CN 201510599913 A CN201510599913 A CN 201510599913A CN 105149611 A CN105149611 A CN 105149611A
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Abstract
The invention relates to a hollow precious metal nanowire as well as a preparation method and application thereof. The method comprises the following steps: taking ascorbic acid as a reducing agent to reduce Pt or Rh and Ag salt to metal atoms; and taking poly (diallyldimethylammonium chloride) as a protective agent, and synthesizing an M-Ag hollow nanowire in one step at the room temperature under a template induction effect of the poly (diallyldimethylammonium chloride) on the growth of a nano material. Meanwhile, the surface of the Pt-Ag or Pd-Ag nanowire is coated with the protective agent, so that the stability and solubility of the Pt-Ag or Pd-Ag nanowire can be greatly improved, and a foundation is set for the application in the field of the biology and the field of catalysis in the future. The M-Ag hollow nanowire prepared by the method is simple in process, high in product yield, uniform and controllable in structure, short in preparation period, and convenient in rapid and mass preparation. The method is easy for controlling the preparation condition, simple in required equipment, relatively high in product preparation success rate and good in industrial application prospect.
Description
Technical field
The invention belongs to noble metal nanometer material technical field, relate to a kind of hollow noble metal nano wire and Synthesis and applications thereof.
Background technology
Noble metal nanometer material has important application prospect in fields such as catalysis, electronics, optics.Wherein, Pt base precious metal nano particle is subject to extensive concern (C.Cui, L.Gan, H.H.Li, S.H.Yu, M.Heggen, P.Strasser.NanoLett.2012,12,5885-5889) owing to having good catalytic activity.The catalytic activity of noble metal nanometer material not only depends on particle size, but also depends on shape, the Nomenclature Composition and Structure of Complexes of material.Due to intermetallic synergic catalytic effect, the performance that the performance of bimetal nano material is more excellent, thus cause the attention (L.Liu, E.Pippel.Angew.Chem.Int.Ed., 2010,50,1 – 6) of Domestic Scientific Research worker.In addition, the noble metal nanometer material of hollow, owing to having large specific area, also show good application prospect at catalytic field.Can infer, many metal hollows nano material probably has better performance.At present, the synthesis of many metals one-dimensional hollow nano material is reacted mainly through Galvanic, usually do template with active metal nano wire or nanometer rods, displacement reaction is there is by Pt or Pd ion and its, obtain many metal nanometer lines (L.Liu, E.Pippel.Angew.Chem.Int.Ed., 2010 of hollow, 50,1 – 6).This method usually needs two steps to carry out, i.e. first step synthesis Ag monodimension nanometer material, and second step carries out Galvanic reaction, and this preparation method's preparation process is more loaded down with trivial details.
Therefore, the technical problem existed at present is that to need to research and develop a kind of preparation process comparatively simple and have the noble metal nano wire Catalysts and its preparation method of higher catalytic activity.
Summary of the invention
Technical problem to be solved by this invention is for the deficiencies in the prior art, provides a kind of hollow noble metal nano wire, and this hollow noble metal nano wire has higher catalytic activity, and preparation method is simple, manufacturing cycle is short, is convenient to quick, a large amount of preparations.
For this reason, the invention provides a kind of hollow noble metal nano wire, it is M-Ag hollow nano wire, and wherein, the mol ratio of M and Ag is (0.1-10): 1; The mol ratio (1-5) of preferred M and Ag: 1; Described M is Pt or Pd.
Present invention also offers a kind of preparation method of above-mentioned hollow noble metal nano wire, it comprises and add M metal precursor, AgNO in protective agent-solvent mixed liquor
3and reducing agent, carry out again after mixing reacting obtained noble metal nano wire.
According to the present invention, M metal precursor and AgNO
3mol ratio be (0.1-10): 1; Preferred M metal precursor and AgNO
3mol ratio be (1-5): 1.The mol ratio of ascorbic acid and M metal precursor is 5:1.
In the present invention, described M metal precursor comprises at least one in Pt salt, Pt acid and Pd salt; Described Pt acid H
2ptCl
6; Described Pt salt is Na
2ptCl
6and/or K
2ptCl; Described Pd salt is K
2pdCl
4and/or Na
2pdCl
4.
In a preferred embodiment of the invention, the temperature of described reaction is 25 DEG C; The described reaction time is 15-20hr; The time of preferred described reaction is 20hr.
In another preferred embodiment of the present invention, in described protective agent-solvent mixed liquor, the volume ratio of protectant aqueous solution and solvent is 1:50.
According to the present invention, in described protectant aqueous solution, described protectant mass concentration is 20% to 35%; Described protective agent is diallyl dimethyl ammoniumchloride.
According to the present invention, described solvent is polyalcohol, and it comprises at least one in ethylene glycol, glycerine, pentanediol and diethylene glycol; Preferred polyol comprises at least one in ethylene glycol, glycerine and pentanediol.
In the present invention, preferred described reducing agent is ascorbic acid.
The present invention still further provides a kind of according to above-mentioned hollow noble metal nano wire as the application of catalyst in electro-catalysis methanol oxidation.
Accompanying drawing explanation
Below in conjunction with accompanying drawing, the present invention is described.
Fig. 1 is the transmission electron microscope photo of hollow Pt-Ag nano wire synthesized in embodiment 1.
Fig. 2 is the transmission electron microscope photo of hollow Pd-Ag nano wire synthesized in embodiment 4.
Fig. 3 is the Electrochemical results characterizing nanowire catalytic activity; Wherein, the result that is oxidized for catalysis methanol of the nano wire of short-term type dotted line to be Pt and the Ag mol ratio in embodiment 7 be 1:1; The result that the nano wire of some line style dotted line to be Pt and Ag mol ratio in embodiment 6 be 5:1 is oxidized for catalysis methanol; Solid line is business Pt catalysis methanol oxidation results.
Detailed description of the invention
For making the present invention easier to understand, describe the present invention in detail below in conjunction with embodiment and accompanying drawing, these embodiments only play illustrative effect, are not limited to range of application of the present invention.
As previously mentioned, the preparation process preparing noble metal nano wire catalyst is comparatively complicated.
Therefore, one aspect of the present invention relates to a kind of hollow noble metal nano wire, and it is M-Ag hollow nano wire, and wherein, the mol ratio of M and Ag is (0.1-10): 1; The mol ratio (1-5) of preferred M and Ag: 1; Described M is Pt or Pd.
In the present invention, the metal M-Ag forming above-mentioned M-Ag hollow nano wire is actually the M-Ag of alloying, i.e. Pt-Ag or Pd-Ag of alloying.
The present invention relates to a kind of preparation method of above-mentioned hollow noble metal nano wire on the other hand, and it comprises and add M metal precursor, AgNO in protective agent-solvent mixed liquor
3and reducing agent, carry out again after mixing reacting obtained noble metal nano wire.
The method that the present invention prepares hollow noble metal nano wire is to utilize co-reducing process, adopts ascorbic acid to make reducing agent, Pt-Ag and the Pd-Ag nano wire of one-step synthesis hollow.
The present invention has investigated different metal salt in the preparation process of hollow noble metal nano wire and has done the impact of presoma, finds that slaine provided by the present invention all may be used for growth M-Ag hollow nano wire.
In certain embodiments of the present invention, M metal precursor and AgNO
3mol ratio be (0.1-10): 1; Preferred M metal precursor and AgNO
3mol ratio be (1-5): 1; The mol ratio of ascorbic acid and M metal precursor is 5:1.
In other embodiments of the present invention, described M metal precursor comprises at least one in Pt salt, Pt acid and Pd salt; Described Pt acid is H
2ptCl
6; Described Pt salt is Na
2ptCl
6and/or K
2ptCl; Described Pd salt is K
2pdCl
4and/or Na
2pdCl
4.
In the present invention, preferred M metal precursor carries out drying process before using.
The present invention has investigated reaction temperature and reaction time in the preparation process of hollow noble metal nano wire and, on the impact of nanowire growth, just can generate hollow noble metal nano wire, and the reaction time has been larger on product structure impact under discovery room temperature condition.
According to certain embodiments of the present invention, the temperature of described reaction is 25 DEG C.The described reaction time is 15-20hr; The time of preferred described reaction is 20hr.
The present inventor studies discovery; in the process of the hollow noble metal nano wire of preparation; protective agent is made with diallyl dimethyl ammoniumchloride; by the template-mediated effect that it grows nano material; Pt or Rh and Ag salt are reduced to metallic atom, thus are grown to serve as one dimension hollow Nano line.Further; in the process of the hollow noble metal nano wire of preparation; with protective agent; such as diallyl dimethyl ammoniumchloride is coated on Pt-Ag or Pd-Ag nanowire surface; greatly can improve the stability of Pt-Ag or Pd-Ag nano wire and water-soluble, for laying the first stone at biological field and catalytic field application in the future.
The present invention has investigated variable concentrations protective agent in the preparation process of hollow noble metal nano wire, the impact that such as diallyl dimethyl ammoniumchloride grows hollow noble metal nano wire, finds that the protective agent of appropriate amount is conducive to growth M-Ag hollow nano wire.Simultaneously, the present invention has also investigated different molecular weight diallyl dimethyl ammoniumchloride in the preparation process of hollow noble metal nano wire and has done protectant impact, finds that different molecular weight diallyl dimethyl ammoniumchloride can as protective agent for growing M-Ag hollow nano wire; Wherein, take molecular weight as the diallyl dimethyl ammoniumchloride of 200,000-100 ten thousand be the best.
According to the inventive method, in described protective agent-solvent mixed liquor, the volume ratio of protectant aqueous solution and solvent is 1:50.
In certain embodiments of the present invention, in described protectant aqueous solution, described protectant mass concentration is 20% to 35%; Described protective agent includes but not limited to diallyl dimethyl ammoniumchloride.
In the present invention, the molecular weight of preferred described diallyl dimethyl ammoniumchloride is 20 ten thousand to 100 ten thousand.
The present inventor also studies discovery, because chloroplatinic acid in course of reaction and diallyl dimethyl ammoniumchloride introduce Cl ion, thus has an effect with the Ag ion that silver nitrate is introduced, generates AgCl; And be that solvent matches with protective agent with polyalcohol, be conducive to AgCl and H
2ptCl
6form the structure of some wire, these linear structures can be used as template for the formation of hollow-core construction.
In the present invention, described solvent is polyalcohol, and it comprises at least one in ethylene glycol, glycerine, pentanediol and diethylene glycol; Preferred polyol is selected from least one in ethylene glycol, glycerine and pentanediol.
In the present invention, described reducing agent is ascorbic acid.
The present invention has investigated different polyalcohol in the preparation process of hollow noble metal nano wire and has done the impact that solvent grows hollow noble metal nano wire, finds that above-mentioned polyalcohol may be used to growth M-Ag hollow nano wire.Wherein, growth M-Ag hollow nano wire is conducive to most with ethylene glycol, glycerine or pentanediol.
In a word, at room temperature, under the protective agent effect of suitable concn, preparation hollow Pt-Ag and Pd-Ag nano wire can be easy to.
The present invention also relates to one according to above-mentioned hollow noble metal nano wire further as catalyst (being called hollow noble metal nano wire catalyst in the present invention) application in electro-catalysis methanol oxidation.
Through experiment, hollow noble metal nano wire of the present invention has higher catalytic activity in electro-catalysis methanol oxidation, is potential fuel battery anode catalyst.
In preferred embodiments more of the present invention, hollow noble metal nano wire to be carried out the step that centrifugal treating and washing obtain pure hollow noble metal nano wire by described method repeatedly after being also included in obtained hollow noble metal nano wire.
In a preferred embodiment of the invention, in above-mentioned steps, centrifugal treating rotating speed is 10000 revs/min.
In another preferred embodiment of the invention, in above-mentioned steps, be preferably that solvent washs with deionized water.
In a specific embodiment of the present invention, M-Ag hollow nano wire of the present invention adopts following steps to prepare:
By the diallyl dimethyl ammoniumchloride mixing and stirring of 20mL polyalcohol and 0.4mL finite concentration and molecular weight, add dried M metal precursor and AgNO
3(M metal precursor and AgNO
3mol ratio be (0.1-10): 1).After mixed liquor stirs, add ascorbic acid (mol ratio of ascorbic acid and M metal precursor is 5:1), stir 20h at a certain temperature, obtain one dimension M-Ag hollow nano wire.
Described polyalcohol is at least one in ethylene glycol, glycerine, pentanediol and diethylene glycol; Preferred polyol is selected from least one in ethylene glycol, glycerine and pentanediol.
Described diallyl dimethyl ammoniumchloride molecular weight is 20 ten thousand to 100 ten thousand.
Described diallyl dimethyl ammoniumchloride mass concentration is 20% to 35%.
Described M metal precursor comprises at least one in Pt salt, Pt acid and Pd salt; Described Pt acid H
2ptCl
6; Described Pt salt is Na
2ptCl
6and/or K
2ptCl; Described Pd salt is K
2pdCl
4and/or Na
2pdCl
4.
Described reaction temperature is room temperature (25 DEG C).
Being dispersed in by pure M-Ag hollow nano wire is loaded with on the copper mesh of carbon film, by its structure of transmission electron microscope observation.
The method of M-Ag hollow nano thread structure is observed: be dispersed in by pure M-Ag hollow nano wire and be loaded with on the copper mesh of carbon film in the present invention, the change of structure before and after growth is observed with transmission electron microscope (JEOL2100F, Jeol Ltd.).
In the present invention, the characterizing method of nanowire catalytic activity is:
The nano wire sample of preparation is collected by centrifugal (10000 revs/min); and then be scattered in 50mL distilled water also again centrifugal; repeat said process three too much protective agents of removing and solvent; then be dispersed in 20mL water; be uniformly dispersed by ultrasonic 30 minutes; getting 20 microlitres drips on glass-carbon electrode, by the organic matter on ion etching removing surface after drying.
Obtained hollow nano wire is used for methanol oxidation test as electrode, and result M-Ag of the present invention hollow nano wire demonstrates has the activity higher than commercial catalysts.
The present invention utilizes co-reducing process, adopts ascorbic acid to make reducing agent, Pt or Rh and Ag salt are reduced to metallic atom; Simultaneously make protective agent with diallyl dimethyl ammoniumchloride, by its template-mediated effect to nano material growth, make M-Ag be grown to serve as one dimension hollow Nano line, thus at room temperature one-step synthesis one dimension M-Ag hollow nano wire.Further; in the process of the hollow noble metal nano wire of preparation; with protective agent; such as diallyl dimethyl ammoniumchloride is coated on Pt-Ag or Pd-Ag nanowire surface; greatly can improve the stability of Pt-Ag or Pd-Ag nano wire and water-soluble, for laying the first stone at biological field and catalytic field application in the future.
Compared with traditional noble metal catalyst, adopt the inventive method to prepare one dimension M-Ag hollow nano wire, technique is simple, Product yields is high, even structure is controlled, and manufacturing cycle is short, is convenient to quick, a large amount of preparations.The condition of the inventive method preparation method easily controls, and equipment needed thereby is simple, and it is higher that product is prepared into power, has good prospects for commercial application.
Embodiment
Embodiment 1: use H
2ptCl
6do Pt source and prepare hollow Pt-Ag nano wire (Pt and Ag mol ratio is 0.12).
At normal temperatures, 2.9mgH is got
2ptCl
6and 10mgAgNO
3be dissolved in 20mL ethylene glycol, add 15mg ascorbic acid, then add 0.4mL diallyl dimethyl ammoniumchloride, after ultrasonic dissolution is complete, standing at room temperature reaction 20h, obtains taupe hollow Pt-Ag nano wire.Reactant liquor in bottle is moved on in centrifuge tube; centrifugal 10 minutes (10000 revs/min); precipitum is scattered in water again; and then centrifugal sedimentation; repeat sedimentation and centrifugal process 3 times; accessory substance in removing solution and excess of solvent and protective agent, finally can obtain pure hollow Pt-Ag nano wire.
Embodiment 2: use Na
2ptCl
6do Pt source and prepare hollow Pt-Ag nano wire (Pt and Ag mol ratio is 0.12).
At normal temperatures, 3.2mgH is got
2ptCl
6and 10mgAgNO
3be dissolved in 20mL ethylene glycol, add 15mg ascorbic acid, then add 0.4mL diallyl dimethyl ammoniumchloride, after ultrasonic dissolution is complete, standing at room temperature reaction 20h, obtains taupe hollow Pt-Ag nano wire.Reactant liquor in bottle is moved on in centrifuge tube; centrifugal 10 minutes (10000 revs/min); precipitum is scattered in water again; and then centrifugal sedimentation; repeat sedimentation and centrifugal process 3 times; accessory substance in removing solution and excess of solvent and protective agent, finally can obtain pure hollow Pt-Ag nano wire.
Embodiment 3: use K
2ptCl
6do Pt source and prepare hollow Pt-Ag nano wire (Pt and Ag mol ratio is 0.12).
At normal temperatures, 3.4mgH is got
2ptCl
6and 10mgAgNO
3be dissolved in 20mL ethylene glycol, add 15mg ascorbic acid, then add 0.4mL diallyl dimethyl ammoniumchloride, after ultrasonic dissolution is complete, standing at room temperature reaction 20h, obtains taupe hollow Pt-Ag nano wire.Reactant liquor in bottle is moved on in centrifuge tube; centrifugal 10 minutes (10000 revs/min); precipitum is scattered in water again; and then centrifugal sedimentation; repeat sedimentation and centrifugal process 3 times; accessory substance in removing solution and excess of solvent and protective agent, finally can obtain pure hollow Pt-Ag nano wire.
Embodiment 4: use Na
2pdCl
4do Pd source and prepare hollow Pd-Ag nano wire (Pd and Ag mol ratio is 1).
At normal temperatures, 16.7mgNa is got
2pdCl
4and 10mgAgNO
3be dissolved in 20mL ethylene glycol, add 99mg ascorbic acid, then add 0.4mL diallyl dimethyl ammoniumchloride, after ultrasonic dissolution is complete, standing at room temperature reaction 20h, obtains taupe hollow Pt-Ag nano wire.Reactant liquor in bottle is moved on in centrifuge tube; centrifugal 10 minutes (10000 revs/min); precipitum is scattered in water again; and then centrifugal sedimentation; repeat sedimentation and centrifugal process 3 times; accessory substance in removing solution and excess of solvent and protective agent, finally can obtain pure hollow Pd-Ag nano wire.
Embodiment 5: use K
2pdCl
4do Pd source and prepare hollow Pd-Ag nano wire (Pd and Ag mol ratio is 1).
At normal temperatures, 20.8mgK is got
2pdCl
4and 10mgAgNO
3be dissolved in 20mL ethylene glycol, add 99mg ascorbic acid, then add 0.4mL diallyl dimethyl ammoniumchloride, after ultrasonic dissolution is complete, standing at room temperature reaction 20h, obtains taupe hollow Pt-Ag nano wire.Reactant liquor in bottle is moved on in centrifuge tube; centrifugal 10 minutes (10000 revs/min); precipitum is scattered in water again; and then centrifugal sedimentation; repeat sedimentation and centrifugal process 3 times; accessory substance in removing solution and excess of solvent and protective agent, finally can obtain pure hollow Pd-Ag nano wire.
Embodiment 6: use H
2ptCl
6do Pt source and prepare hollow Pt-Ag nano wire (Pt and Ag mol ratio is 1).
At normal temperatures, 5.8mgH is got
2ptCl
6and 2mgAgNO
3be dissolved in 20mL ethylene glycol, add 15mg ascorbic acid, then add 0.4mL polyallyl alkyl dimethyl ammonium chloride, after ultrasonic dissolution is complete, standing at room temperature reaction 20h, obtains taupe hollow Pt-Ag nano wire.Reactant liquor in bottle is moved on in centrifuge tube; centrifugal 10 minutes (10000 revs/min); precipitum is scattered in water again; and then centrifugal sedimentation; repeat sedimentation and centrifugal process 3 times; accessory substance in removing solution and excess of solvent and protective agent, finally can obtain pure hollow Pt-Ag nano wire.
Embodiment 7: use H
2ptCl
6do Pt source and prepare hollow Pt-Ag nano wire (Pt and Ag mol ratio is 5).
At normal temperatures, 29mgH is got
2ptCl
6and 2mgAgNO
3be dissolved in 20mL ethylene glycol, add 15mg ascorbic acid, then add 0.4mL polyallyl alkyl dimethyl ammonium chloride, after ultrasonic dissolution is complete, standing at room temperature reaction 20h, obtains taupe hollow Pt-Ag nano wire.Reactant liquor in bottle is moved on in centrifuge tube; centrifugal 10 minutes (10000 revs/min); precipitum is scattered in water again; and then centrifugal sedimentation; repeat sedimentation and centrifugal process 3 times; accessory substance in removing solution and excess of solvent and protective agent, finally can obtain pure hollow Pt-Ag nano wire.
Hollow Pt-Ag obtained by above-described embodiment or Pd-Ag nano wire are used for methanol oxidation test as electrode, and result M-Ag of the present invention hollow nano wire demonstrates has the activity higher than commercial catalysts.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. a hollow noble metal nano wire, it is M-Ag hollow nano wire, and wherein, the mol ratio of M and Ag is (0.1-10): 1; The mol ratio (1-5) of preferred M and Ag: 1; Described M is Pt or Pd.
2. a preparation method for hollow noble metal nano wire as claimed in claim 1, it comprises and add M metal precursor, AgNO in protective agent-solvent mixed liquor
3and reducing agent, carry out again after mixing reacting obtained noble metal nano wire.
3. preparation method according to claim 2, is characterized in that, M metal precursor and AgNO
3mol ratio be (0.1-10): 1; Preferred M metal precursor and AgNO
3mol ratio be (1-5): 1; The mol ratio of ascorbic acid and M metal precursor is 5:1.
4. the preparation method according to Claims 2 or 3, is characterized in that, described M metal precursor comprises at least one in Pt salt, Pt acid and Pd salt; Described Pt acid H
2ptCl
6; Described Pt salt is Na
2ptCl
6and/or K
2ptCl; Described Pd salt is K
2pdCl
4and/or Na
2pdCl
4.
5. the preparation method according to Claims 2 or 3, is characterized in that, the temperature of described reaction is 25 DEG C; The described reaction time is 15-20hr; The time of preferred described reaction is 20hr.
6. according to the preparation method in claim 2-5 described in any one, it is characterized in that, in described protective agent-solvent mixed liquor, the volume ratio of protectant aqueous solution and solvent is 1:50.
7. the preparation method according to claim 2-5, is characterized in that, in described protectant aqueous solution, described protectant mass concentration is 20% to 35%; Described protective agent is diallyl dimethyl ammoniumchloride.
8. the preparation method according to claim 2-5, is characterized in that, described solvent is polyalcohol, and it comprises at least one in ethylene glycol, glycerine, pentanediol and diethylene glycol; Preferred polyol comprises at least one in ethylene glycol, glycerine and pentanediol.
9. according to the preparation method in claim 2-5 described in any one, it is characterized in that, described reducing agent is ascorbic acid.
10. hollow noble metal nano wire according to claim 1 is as the application of catalyst in electro-catalysis methanol oxidation.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106041115A (en) * | 2016-05-26 | 2016-10-26 | 华南理工大学 | Sodium alga acid/silver nanowire sol and preparation method thereof |
| CN106784880A (en) * | 2017-01-19 | 2017-05-31 | 山东大学 | The synthetic method of water-soluble one-dimensional rhotanium nano wire |
| CN108500256A (en) * | 2018-05-07 | 2018-09-07 | 南京师范大学 | The hollow porous PdRh nano bowls preparation method of one kind and its resulting materials and application |
| CN108714421A (en) * | 2018-05-11 | 2018-10-30 | 华南理工大学 | A kind of Pt@Ag hollow structure nano particle elctro-catalysts and preparation and application |
| CN109270046A (en) * | 2018-08-30 | 2019-01-25 | 东南大学 | A kind of construction method of the controllable micro-nano array based on gold and silver nano brick and its application |
| CN110299222A (en) * | 2019-07-29 | 2019-10-01 | 中国工程物理研究院应用电子学研究所 | A kind of visible transparent conductive film and preparation method thereof |
| CN111922359A (en) * | 2020-10-19 | 2020-11-13 | 西安宏星电子浆料科技股份有限公司 | Preparation method of pure silver nanowires |
| CN115533090A (en) * | 2022-09-28 | 2022-12-30 | 南京航空航天大学 | Hollow rhodium nano structure and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009011658A1 (en) * | 2007-07-18 | 2009-01-22 | Nanyang Technological University | Hollow porous microspheres |
| CN101503766A (en) * | 2009-03-18 | 2009-08-12 | 山东大学 | Hollow porous tubular structured gold nano material and preparation thereof |
| CN103857484A (en) * | 2012-05-11 | 2014-06-11 | Lg化学株式会社 | Method for manufacturing hollow metal nanoparticles, and hollow metal nanoparticles manufactured thereby |
| CN103990793A (en) * | 2014-05-09 | 2014-08-20 | 北京威士恩科技有限公司 | High-length-to-diameter-ratio solid-walled hollow gold/gold-silver nanotube and manufacturing method thereof |
| CN104874790A (en) * | 2015-06-10 | 2015-09-02 | 苏州冷石纳米材料科技有限公司 | Gold nano material adopting porous tubular hollow structure and preparation method of gold nano material |
| CN104884194A (en) * | 2012-12-27 | 2015-09-02 | Lg化学株式会社 | Hollow metal nanoparticle supported by support body |
| CN105261766A (en) * | 2015-09-09 | 2016-01-20 | 华侨大学 | PdAg alloy nanotube positive catalyst of direct direct ethanol fuel cell and preparation method of PdAg alloy nanotube positive catalyst |
-
2015
- 2015-09-18 CN CN201510599913.4A patent/CN105149611B/en not_active Expired - Fee Related
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009011658A1 (en) * | 2007-07-18 | 2009-01-22 | Nanyang Technological University | Hollow porous microspheres |
| CN101503766A (en) * | 2009-03-18 | 2009-08-12 | 山东大学 | Hollow porous tubular structured gold nano material and preparation thereof |
| CN103857484A (en) * | 2012-05-11 | 2014-06-11 | Lg化学株式会社 | Method for manufacturing hollow metal nanoparticles, and hollow metal nanoparticles manufactured thereby |
| CN104884194A (en) * | 2012-12-27 | 2015-09-02 | Lg化学株式会社 | Hollow metal nanoparticle supported by support body |
| CN103990793A (en) * | 2014-05-09 | 2014-08-20 | 北京威士恩科技有限公司 | High-length-to-diameter-ratio solid-walled hollow gold/gold-silver nanotube and manufacturing method thereof |
| CN104874790A (en) * | 2015-06-10 | 2015-09-02 | 苏州冷石纳米材料科技有限公司 | Gold nano material adopting porous tubular hollow structure and preparation method of gold nano material |
| CN105261766A (en) * | 2015-09-09 | 2016-01-20 | 华侨大学 | PdAg alloy nanotube positive catalyst of direct direct ethanol fuel cell and preparation method of PdAg alloy nanotube positive catalyst |
Non-Patent Citations (3)
| Title |
|---|
| FRANICS P.ZAMBORINI等: "《Twin Plane Decoration of Silver Nanorods with Palladium by Galvanic Exchange at a controled Rate》", 《LANGMUIR》 * |
| SIMONA E.HUNYADI等: "《Synthesis and Characterization of Silver-Platinum Bimetallic Nanowires and Platinum nanotubes》", 《J CLUST SCI》 * |
| XINGLIANG LI等: "《The unusual effect of AgNO3 on the growth of Au nanostructures and their catalytic performance》", 《NANOSCALE》 * |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106041115A (en) * | 2016-05-26 | 2016-10-26 | 华南理工大学 | Sodium alga acid/silver nanowire sol and preparation method thereof |
| CN106784880A (en) * | 2017-01-19 | 2017-05-31 | 山东大学 | The synthetic method of water-soluble one-dimensional rhotanium nano wire |
| CN106784880B (en) * | 2017-01-19 | 2019-06-28 | 山东大学 | The synthetic method of water-soluble one-dimensional rhotanium nano wire |
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| CN108714421A (en) * | 2018-05-11 | 2018-10-30 | 华南理工大学 | A kind of Pt@Ag hollow structure nano particle elctro-catalysts and preparation and application |
| CN108714421B (en) * | 2018-05-11 | 2021-05-14 | 华南理工大学 | Pt @ Ag hollow-structure nanoparticle electrocatalyst, preparation method and application |
| CN109270046A (en) * | 2018-08-30 | 2019-01-25 | 东南大学 | A kind of construction method of the controllable micro-nano array based on gold and silver nano brick and its application |
| CN110299222A (en) * | 2019-07-29 | 2019-10-01 | 中国工程物理研究院应用电子学研究所 | A kind of visible transparent conductive film and preparation method thereof |
| CN110299222B (en) * | 2019-07-29 | 2020-09-18 | 中国工程物理研究院应用电子学研究所 | Visible light transparent conductive film and preparation method thereof |
| CN111922359A (en) * | 2020-10-19 | 2020-11-13 | 西安宏星电子浆料科技股份有限公司 | Preparation method of pure silver nanowires |
| CN111922359B (en) * | 2020-10-19 | 2021-01-05 | 西安宏星电子浆料科技股份有限公司 | Preparation method of pure silver nanowires |
| CN115533090A (en) * | 2022-09-28 | 2022-12-30 | 南京航空航天大学 | Hollow rhodium nano structure and preparation method thereof |
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